Preparation, characterization, esr and pas studies of Cu0.5NbAlp3O12 (CNP) and HnbAlp3O12 (HNP)

ABSTRACT

The present invention relates to the process of preparation and characterization of novel sodium superionic conductor (NASICON) type niobium aluminium phosphate of formula Cu0.5NbAlP 3 O 12  (CNP), HNbAlP 3 O 12 (HNP) and to study its Electron Spin Resonance (ESR) and Photo Acoustic (PA) spectra.

FIELD OF THE INVENTION

[0001] The present invention relates to the process of preparation, characterization, electron spin resonance (ESR) and photo acoustic (PA) studies of Cu_(0.5)NbAlp₃O₁₂ (CNP) and HnbAlp₃O₁₂ (HNP).

BACKGROUND AND PRIOR ART TO THE INVENTION

[0002] Sodium super ionic conductor (NASICON) and related sodium zirconium phosphate NaZr₂P₃O₁₂ (NZP) and niobium titanium phosphate NbTiP₃O₁₂ are well studied [1-6] due to their important proper-J ties of (i) low thermal expansion behavior [5-9], (ii) fast ionic conductivity [2] and (iii) high temperature I stability [2]. They are used as heat exchangers and I mirror blanks for space technology, catalyst supports, high temperature fuel cells, possible host for radioactive waste and as humidity and gas sensors [10-15]. Their general formula is AMM′P₃O₁₂ where, ‘A’ can be alkali, alkaline earth or Cu²⁺ion, M and M′ can be tri-, tetra- or pentavalent transition metal ion. The structure is characterized by corner sharing of PO₄ tetrahedra with MO₆, (and M′0 ₆,) octahedrai [16,17]. The three dimensionally linked interstitial′ space can accommodate ions as H⁺ or as large as I Cs+ This space can also remain vacant as in NbTiP₃O₁₂ [18]. The structure is flexible for substitution at A, M or M′ sites, giving rise to a large number of closely related compounds. Among the NASICONs, copper NASICONs are relatively less|investigated [19-22]. In this paper, we report the preparation, characterization, electron spin resonance (ESR) and photo acoustic (PA) studies of Cu0.5-NbAlP₃O₁₂ (CNP) and HnbAlP₃O₁₂ (HNP).

[0003] A reference may be made to P. Vashishta. J. N. Mundy, O. K. Shenoy (Eds.). Proceedings of International Conference on Fast Ion Transport in Solids, Lake Geneva, North-Holland, Amsterdam, 1979.

[0004] Another reference may be made to J. B. Goodenough. H. Y. P. Hong, J. A. Kafalas. Mater. Res. Bull. 11(1976)203.

[0005] Still another reference may be made to H. Y. P. Hong. Mater. Res. Bull. 11 (1976) 176.

[0006] Yet another reference may be made to J. Alamo, R. Roy, J. Am. Ceram. Soc. 67 (1984) C78.

[0007] One more reference may be made to T. Oota, I. Yamai. J. Am. Ceram. Soc. 69 (1986) 1.

[0008] One another reference may be made to R. Roy. D. K. Agrawal. R. A. Roy. Mater. Res. Bull. 19 (1984)471.

[0009] Another reference may be made to D. K. Agrawal, V. S. Stubican, Mater. Res. Bull. 20 (1985) 99.

[0010] Still another reference may be made to G. E. Lenain. H. A. McKinstry. S. Y. Limaye, A. Woodword, Mater. Res. Bull. 19 (1984) 1451.

[0011] Yet another reference may be made to S. Y. Limaye. D. K. Agrawal. H. A. Mckinstry. J. Am. Ceram. Soc. 70(1987) C232.

[0012] One more reference may be made to D. K. Agrawal. J. H. Adair, J. Am. Chem. Soc. 71 (1990) 2153.

[0013] One another reference may be made to R. Roy. E. R. Vance. J. Alamo. Mater. Res. Bull. 17 (1982) 585.

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[0015] Still another reference may be made to Y. Hideaki. S. Takehiko, Sens. Actuators, B 5 (1991) 135.

[0016] Yet another reference may be made to Y. Sheng. S. Youichi. M. Norrio, Y. Nobru, Chem. Lett. 47; (1992) 587.

[0017] One more reference may be made to Y. Sheng, H. Sanchio, S. Youichi, M. Norrio. F. Hozumi. Y. I Nobru. Chem. Lett. 46 (1991) 2069.;

[0018] One another reference may be made to L. O. Hagman, P. Kierkegaard. Acta Chem. Scand. 22 (1968) 1822.

[0019] Another reference may be made to M. Sljukic. B. Matkovic, B. Prodic, Z. Kristallogr. 130 (1968)1872.

[0020] Still another reference may be made to R. Masse, A. Durif, J. C. Guitel, I. Tordjman. Bull. Soc. Fr.Mineral. Cristallogr. 95 (1972) 47.

[0021] Yet another reference may be made to P. C. Yao, D. J. Fray. Solid State lonics 8 (1983) 35.

[0022] One more reference may be made to A. El Jazouli, J. L. Soubeyroux, J. M. Dance, G. Le Flem, J. Solid State Chem. 65 (1986) 351.

[0023] One another reference may be made to A. El Jazouli. M. Alami. R. Brochu. J. M. Dance, G. Le Flem, P. Hagenmuller. J. Solid State Chem. 71 (1987) 444.

[0024] Another reference may be made to G. Le Polles, A. El Jazouli, R. Olazcuaga, J. M. Dance. G. Le Flem. P. Hagenmuller. Mater. Res. Bull. 22 (1987) 1171.

[0025] Still another reference may be made to J. R. Pilbrow, Transition Ion Electron Paramagnetic Resonance, Oxford Science Publications. 1990, Chap 5.

[0026] Yet another reference may be made to A. Clearfield, B. D. Roberts, M. A. Subramanian, Mater. Res. Bull. 19(1984)219.

OBJECTS OF THE INVENTION

[0027] The main object of the present invention is to provide a process of preparation, characterization, electron spin resonance (ESR) and photo acoustic (PA) studies of Cu_(0.5)NbAlP₃O₁₂ (CNP) and HNbAlP₃O₁₂ (HNP).

[0028] Another object of the present invention relates to a novel sodium superionic conductor (nasicon) type niobium aluminium phosphate and a method for preparation of the same

[0029] Still another object of the present invention is to characterize the above said compound.

[0030] Yet another object of the present invention is to study the electron spin resonanace (ESR) and photoacoustic (PA) characters of the said compound.

SUMMARY OF THE INVENTION

[0031] The present invention relates to the process of preparation, characterization, electron spin resonance (ESR) and photo acoustic (PA) studies of compounds Cu_(0.5)NbAlP₃O₁₂ (CNP) and HNbAlP₃O₁₂ (HNP).

DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0032] In the drawings accompanying the specification,

[0033]FIG. 1 represent the Powder X-ray diffractogram of (a) CNP and (b) HNP.

[0034]FIG. 2 represent the room temperature electron spin resonance spectra of (a) CNP, (b) simulated ESR spectra of CNP, (c) CNP heated at 450° C. and (d) HNP.

[0035]FIG. 3 represent the PA spectra of (a) CNP and (b) HNP.

DETAILED DESCRIPTION OF THE INVENTION

[0036] In an embodiment, the present invention relates to the process of preparation, characterization, electron spin resonance (ESR) and photo acoustic (PA) studies of a novel sodium super ionic conductor (NASICON) type niobium aluminum phosphates of the composition Cu_(0.5)NbAlP₃O₁₂ (CNP) and HNbAlP₃O₁₂ (HNP).

[0037] In one embodiment, the said compounds are isomorphous with NbTiP₃O₁₂ and unit cell parameters are evaluated. Copper and hydrogen occupy the channels. Reduction of CNP gives rise of HNP. Electron spin resonance (ESR) and photo acoustic (PA) spectral data are consistent with elongated octahedral configuration around Cu²⁺ ion.

[0038] In another embodiment, CNP is prepared by mixing stoichiometric amounts of Nb₂O₅, Al₂O₃, NH₄H₂PO₄ and Cu(NO₃)₂3H₂O (all are analytical′ reagents obtained from SD chemicals) in a mortar with spectral grade acetone (SD chemicals). The resultant powder was sequentially heated at 500° C. (3 h), 750° C. (3 h) and finally 1075° C. (5 h). This process resulted Cu0.5NbAlP₃O₁₂(CNP) as a light green compound.

[0039] In yet another embodiment HNP is prepared from CNP by placing it in a ceramic boat and reducing at 400° C. and 550° C. (4 h each) by passing hydrogen gas in a tube furnace. The compound obtained by reducing at 550° C. was HNP and was light black in color.

[0040] In a yet another embodiment, density of CNP was experimentally determined using xylene as the immersion liquid. Powder X-ray diffractograms were recorded on Siemens D-4000 using CuK_(α) radiation (λ=1.506 Å). The unit cell parameters are derived by using a computer programme by providing d and hkl values as input parameters.

[0041] In still yet another embodiment, room temperature ESR spectra were recorded on a JEOL PE-3×-band spectrometer equipped with a 100 kHz field modulation unit. DPPH was used as standard. The powder ESR spectrum of CNP was simulated using a computer programme [23]. The “g”, “a” and line width are given as input parameters. Room temperature emission spectra were recorded by Hitachi-3010 spectrofluorometer.

[0042] In still yet another embodiment, PA spectra were recorded on an extensively modified OAS-400 PA spectrometer (EDT Research, London). The light beam from a 300-W xenon lamp was intensity-modulated using a continuously variable mechanical chopper (HMS 222, NY) operating at a chopping frequency of 40 Hz. The signals were recorded using a B and K 4165 microphone (Bruel and Kjaer, Naerum, Denmark) coupled to a power supply (B and K 2804). The sensitivity of the microphone was 40 mV/Pa. The signal was processed through a preamplifier (EG and G 113); Princeton applied Research, Princeton, N.J.) and a lock-in analyzer EG and G 7620. Normalization of the spectra to constant input light intensity was achieved by using the PA spectrum of carbon black.

[0043] Powder XRD of CNP was found to be free from impurities. It is found to be isomorphous with NbTiP₃O₁₂ [18]. All the d-lines are indexed and the unit cell parameters are evaluated using a computer programme. The observed and calculated d-values are given in Table 1. The unit cell parameters are shown in Table 2 along with the unit cell parameters of related systems. The powder XRD of HNP was found to be similar to that of CNP, except for the intensities. The reflections of various hkl planes of HNP were less intense than CNP (FIG. 1). All the d-lines are indexed and the unit cell parameters are derived (Tables 1 and 2). From Table 2, it is clear that the unit cell parameters of CNP and HNP are very close to each other. Since both Cu²⁺ and H⁺ occupy the channels, the basic skeleton remains the same and, hence, the “a” and “c” parameters are close to each other. The observed change in the intensities may be due to the difference in the number of electrons present in Cu²⁺ and H⁺. TABLE 1 Experimental and calculated d-values and of CNP and HNP CNP HNP h k l d_(obs) d_(cal) d_(obs) d_(cal) 1 0 2 6.096 6.125 6.127 6.127 1 0 4 4.383 4.405 4.407 4.406 1 1 0 — 4.261 4.283 4.262 1 1 3 3.678 3.682 3.691 3.683 2 0 4 3.147 3.063 3.065 3.063 1 1 6 2.770 2.776 2.778 2.777 1 0 8 — 2.573 — 2.573 2 1 4 2.480 2.486 2.484 2.487 3 0 0 — 2.460 — 2.461 2 0 8 2.239 2.202 2.215 2.203 1 1 9 2.108 2.117 2.120 2.118 2 1 7 2.089 2.084 2.078 2.085 2 2 3 2.046 2.045 — 2.046 3 0 6 2.014 2.041 — 2.042 3 1 2 2.014 2.012 2.013 2.013 2 1 8 1.954 1.956 1.962 1.957 3 1 4 1.918 1.917 1.920 1.918 2 0 10 1.895 1.887 — 1.887 2 2 6 1.841 1.841 1.845 1.841 4 0 2 — 1.819 — 1.820 2 1 10 1.721 1.725 1.726 1.726 3 1 7 — 1.714 — 1.714 1 1 12 1.679 1.681 1.679 1.681 3 1 8 1.642 1.641 1.640 1.641 3 2 4 1.616 1.617 1.617 1.618 4 1 0 1.590 1.610 3 2 5 1.575 1.579 4 1 3 — 1.572 4 0 8 1.528 1.531 3 1 10 1.496 1.497

[0044] TABLE 2 Unit cell parameters of CNP, HNP and related systems α (A) c (A) d_(obs) (g cm⁻³) d_(cal) (g Refer- Compound ⊥ 0.02 ⊥ 0.02 ⊥ 0.02 cm⁻³) ence Cu_(0.5)Zr₂P₃O₁₂ 8.84 22.77 3.24 ⊥ 0.20.02 3.23 [21] H_(0.5)Cu_(0.5)Zr₂P₃O₁₂ 8.84 22.75 — — [22] u_(0.5)NbAlP₃O₁₂ 8.522 21.964 4.035-⊥ 0.02 4.05 This work HNbAlP₃O₁₂ 8.526 21.966 — 3.90 This work HZr2P₃O₁₂ 8.80 23.23 — — [24] Cu_(0.5)Ti₂P₃O₁₂ 8.41 21.88 3.05 ⊥ 0.01 3.07 [20]

[0045] Room temperature X-band powder ESR spectrum of CNP and its reduced product at 400° C. and 550° C. are shown in FIG. 2. The ESR spectrum of CNP is characterized by a broad unresolved band at lower magnetic field and a sharp one on the higher field side (FIG. 2a). This spectrum is similar to that of Cu_(0.5)Ti₂P₃O₁₂ [20.21]. The g values are derived and shown in Table 3. Since g₁₁>⊥, the unpaired electron is in d_(x) ²-y², which corresponds to the John-Teller distortion involving an elongated octahedral configuration around Cu²⁺ ion. Similar results were obtained for other related systems [20,21]. The room temperature powder ESR spectrum of CNP is simulated using a computer programme (FIG. 2b). The ESR spectrum of the sample of reduced product at 400° C. was found to be identical to that of CNP, except for the intensities (FIG. 2c). The compound reduced at 550° C. did not give any ESR signal (FIG. 2d).

[0046] In copper NASICON type phosphates, Cu⁺² ion occupy the channels [21]. In reducing with hydrogen, CNP can give rise to (i) H_(0.5)Cu_(0.5)(I)NbAlP₃O₁₂ or (ii) HnbAlP₃O₁₂ or a mixture of both. The samples reduced at 400° C. and 550° C. were subjected to fluorescence measurement by exciting at 287 nm. No signal was observed around 450-700 nm unlike H_(0.5)Cu_(0.5)(I)Zr₂P₃O₁₂ [22). Copper (I) hydrogen NASICONs, when heated in air, are known to give copper (II) NASICONs expelling the hydrogen [22]. When the sample (CNP) reduced at 550° C. is heated in air and subjected to ESR, no signal was observed. This rules out the formation of II_(0.5)Cu_(0.5)(I)NbAIP₃O₁₂. Therefore, the compound formed when CNP is reduced at 550° C. is unambiguously identified at HNbAIPO₁₂. TABLE 3 The g value of some NASICON type phosphates Sample g_(∥) g_(⊥) g_(av) T (K) Reference NaTi₂P₃O₁₂:Cu²⁺ 2.366 2.072 2.174 300 [20] CuTi₂P₃O₁₂:Cu²⁺ 2.36  2.06  2.164 300 [20] CaTi₂P₃O₁₂:Cu²⁺ 2.37  2.06  2.168 300 [20] Cu_(0.5)Ti2P₃O₁₂ 2.33  2.067 2.158 300 [20] Cu_(0.5)NbAIP₃O₁₂ 2.366 2.10  2.192 300 this work HNbAIP₃O₁₂ — — — 300 this work

[0047] In yet another embodiment, the PA spectra of CNP and HNP are recorded in the range 210-800 nm (FIG. 3). The PA spectrum of CNP consists of broad band around 250-400 nm and of another broad band above 600 nm (FIG. 3a). PA spectrum of HNP is characterized by broad band around 300-450 nm. No band is observed above 600 nm (FIG. 3b).

[0048] In still another embodiment, the optical spectrum of copper NASICONs is characterized by a broad band of around 200-400 nm and of another between 600 and 1100 nm [20-22]. The broad band (200-400 nm) is due to phosphate group and its location is independent of the nature of the cation. The broad band in the region 60-1100 nm is due to d-d transitions [20-22]. The PA spectrum of CNP is identical to the reflectance spectrum of Cu_(0.5)Zr₂P₃ O₁₂ [21]. We could record PA spectrum up to 800 nm only due to instrumental constraints. However, the profile of the spectrum shows the transitions due to phosphates group and d-d transitions of Cu²⁺ (3d⁹) in high spin octahedral configuration. The broad band observed in the PA spectrum of HNP in the region 300-450 nm is due the phosphate group. The absence of band above 600 nm indicates the absence of Cu²⁺ ions in HNP.

[0049] In a further embodiment, the possible mechanism for the formation of HNbAIPO₁₂ is as follows. When CNP is heated with hydrogen at various temperature Cu²⁺ ions are reduced to elemental copper and are coming out of the channels. Once the reduction is complete, the compound becomes light black, since it is a mixture of Cu and HNbAIPO₁₂. This black mixture, when dissolved in dilute nitric acid, gives a blue color solution and white solid. The powder XRD of both black mixture and white solid are identical. Thus, the white solid is HNbAIPO₁₂. The sequence of reactions can be written as

[0050] The invention is described by the following examples, which should not be construed as limitations to the scope of the invention.

EXAMPLES 1

[0051] In another embodiment, CNP is prepared by mixing stoichiometric amounts of Nb2O₅, Al₂O₃, NH₄H₂PO₄ and Cu(NO₃)₂3H₂O (all are analytical reagents obtained from SD chemicals) in a mortar with spectral grade acetone (SD chemicals). The resultant powder was sequentially heated at 500° C. (3 h), 750° C. (3 h) and finally 1075° C. (5 h). This process resulted Cu0.5NbAlP₃O₁₂(CNP) as alight green compound.

EXAMPLES 2

[0052] In yet another embodiment HNP is prepared from CNP by placing it in a ceramic boat and reducing at 400° C. and 550° C. (4 h each) by passing hydrogen gas in a tube furnace. The compound obtained by reducing at 550° C. was HNP and was light black in color 

We claim:
 1. Novel compounds as sodium super ionic conductor (NASICON) type of formula Cu_(0.5)Nb Al P₃O₁₂[CNP] and HnbAlP₃O₁₂[HNP]
 2. Compounds as claimed in claim 1 have the following characteristic features. a) Experimental and calculated d-values and of CNP and HNP CNP HNP h k l d_(obs) d_(cal) d_(obs) d_(cal) 1 0 2 6.096 6.125 6.127 6.127 1 0 4 4.383 4.405 4.407 4.406 1 1 0 — 4.261 4.283 4.262 1 1 3 3.678 3.682 3.691 3.683 2 0 4 3.147 3.063 3.065 3.063 1 1 6 2.770 2.776 2.778 2.777 1 0 8 — 2.573 — 2.573 2 1 4 2.480 2.486 2.484 2.487 3 0 0 — 2.460 — 2.461 2 0 8 2.239 2.202 2.215 2.203 1 1 9 2.108 2.117 2.120 2.118 2 1 7 2.089 2.084 2.078 2.085 2 2 3 2.046 2.045 — 2.046 3 0 6 2.014 2.041 — 2.042 3 1 2 2.014 2.012 2.013 2.013 2 1 8 1.954 1.956 1.962 1.957 3 1 4 1.918 1.917 1.920 1.918 2 0 10 1.895 1.887 — 1.887 2 2 6 1.841 1.841 1.845 1.841 4 0 2 — 1.819 — 1.820 2 1 10 1.721 1.725 1.726 1.726 3 1 7 — 1.714 — 1.714 1 1 12 1.679 1.681 1.679 1.681 3 1 8 1.642 1.641 1.640 1.641 3 2 4 1.616 1.617 1.617 1.618 4 1 0 1.590 1.610 3 2 5 1.575 1.579 4 1 3 — 1.572 4 0 8 1.528 1.531 3 1 10 1.496 1.497

b) unit cell parameters of CNP and HNP α (A) c (A) D_(obs) (g cm⁻³) d_(cal) (g Compound ⊥ 0.02 ⊥ 0.02 ⊥ 0.02 cm⁻³) Cu_(0.5)NbAlP₃O₁₂ 8.522 21.964 4.035-⊥ 0.02 4.05 HNbAlP₃O₁₂ 8.526 21.966 — 3.90

c) g values of some NASICON type phosphates Sample g_(∥) g_(⊥) g_(av) T (K) i) Cu_(0.5)NbAIP₃O₁₂ 2.366 2.10 2.192 300 ii) HNbAIP₃O₁₂ — — — 300


3. Compounds as claimed in claim 1, wherein the density CNP is determined using Xylene immersion liquid.
 4. Compounds as claimed in claim 1, wherein powdered XRD of CNP and HNP are similar except for intensities of various like plants.
 5. Compounds as claimed in claim 1 wherein the unit cell parameters of CNP and HNP are very close to each other.
 6. Compounds as claimed in claim 1 wherein photoacoustic spectra of CNP is characteristic by broad band around a wave length of 250-400 nm and another broad band around a wave length of 250-400 nm and another broad band above 600 nm.
 7. Compounds as claimed in claim 1 wherein the photo acoustic spectrum of HNP is characterized by a broad band around a wavelength of 300-450 nm.
 8. Compounds as claimed in claim 1 wherein CNP obtained is light green colored and HNP obtained is light black or white colored by treating with nitric acid.
 9. A process for preparation of compounds of claim 1, the said process comprises steps of: a) mixing a stoichiometric amounts of Nb₂O₅, Al₂O₃, NH₄H₂PO₄ and Cu (NO₃)₂3H₂O ( all analytical grade) in presence of spectral grade organic solvent to obtain a powder, b) heating the powder of step (a) sequentially to 500° C. for a period of 3-4 hrs, followed by 750° C. for a period of 5-6 hrs to obtain Cu0.5NbAlPO₃O₁₂[CNP] as a light green solid. c) reducing the solid of step (b) in a ceramic boat using a stream of hydrogen gas in a tube furnace by heating to 400° C. for a period of 3-4 hrs and finally to 550° C. for 3-4 hrs to obtain HnbAlP₃O₁₂[HNP) as a light black solid. d) treating optionally the solid of step (c) with nitric acid to obtain a solution containing solid, and e) separating the solid of step (d) from the solution to obtain white colored HNbAlP₃O₁₂(HNP). 